Lubricant composition

ABSTRACT

LUBRICANT COMPOSITIONS COMPRISING A MAJOR AMOUNT OF A LUBRICATING BASE FLUID AND A MINOR AMOUNT OF EXTREME PRESSURE ADDITIVES WHICH CONTAIN EITHER A METHYLENE, MONOHALOMETHYLENE OR DIHALOMETHYLENE GROUP BETWEEN TWO MOIETIES SELECTED FROM THE GROUP CONSISTING OF PHOSPHONO, DIHYDROCARBYLPHOSPHORYL, PHENYL, SUBSTITUTED PHENYL, KETO, CYANO, AND CARBOXYLATE ESTER MOIETIES.

United States Patent 01 :"fice 3,579,449 Patented May 18, 1971 3,579,449 LUBRICANT COMPOSITION Robert Earl Wann, Denzel Allan Nicholson, and Ted Joe Logan, Hamilton, Ohio, assignors to the Procter & Gamble Company, Cincinnati, Ohio No Drawing. Filed Sept. 26, 1968, Ser. No. 762,966 Int. Cl. Cm 1/46, 1/30 U.S Cl. 252-495 8 Claims ABSTRACT OF THE DISCLOSURE Lubricant compositions comprising a major amount of a lubricating base fluid and a minor amount of extreme pressure additives which contain either a methylene, monohalomethylene or dihalomethylene group between two moieties selected from the group consisting of phosphono, dihydrocarbylphosphoryl, phenyl, substituted phenyl, keto, cyano, and carboxylate ester moieties.

BACKGROUND OF THE INVENTION (1) Field of the invention (2) Prior art Halogen substituted compounds having phosphonate ester and carboxylate ester moieties are known as additives for lubricant compositions. See, for example, US. Pats. 2,725,359; 2,599,761; 3,296,138; 2,225,366; 2,882,- 303-316; 2,824,839; 2,993,859; 2,722,515; 2,767,142; 2,882,228; and 2,848,475. However, the search has continued for effective extreme pressure lubricant additives and especially for such additives which are simple compounds that can be made economically and which do not cause excessive corrosion problems.

THE INVENTION This invention relates to lubricant compositions comprising (1) a major amount of a lubricating base fluid and (2) a minor amount suflicient to increase the loadbearing properties of said compositions of a compound having the formula:

wherein each X is selected from the group consisting of hydrogen, chlorine, iodine and bromine atoms, each Y is selected from the group consisting of moieties having the following formulas wherein each R is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkenyl, haloalkyl, haloaryl, haloalkaryl, haloaralkyl, haloalkenyl and nitroaryl moieties containing from 1 to about 22 carbon atoms and each R is selected from the group consisting of R, a halogen atom and a hydrogen atom, the above selections being made so that both Xs can be hydrogen atoms only when both Ys are and that one X can be hydrogen only when each Y is selected from the group consisting of THE LUBRICATING BASE FLUID The extreme pressure additives of this invention will impart improved load-bearing characteristics to a wide variety of base fluids which are used for a variety of purposes. Broadly, the base fluid can be either a petroleum hydrocarbon, a fatty acid triglyceride, a synthetic fluid, an aqueous based fluid, or mixtures thereof. Petroleum hydrocarbons include mineral oil (including light solvents, neutral oils, heavy, bright and refined stocks, and asphaltic residual stocks), greases and waxes. The lubricating base fluid can also comprise suspensions of graphite in oils. Synthetic fluids include such disparate materials as polymerized olefins, organic carbonates, organic esters and/or ethers, polyglycols, silicones, modified organic materials (halogenated, phosphated, sulfurized, etc.) polymers, e.g., alkylmethacrylate polymers and synthetic resins, e.g., resins formed by esterification of polyhydric alcohols with polycarboxylic acids. Examples of base fluids which can be used in the practice of this invention include those disclosed in US. Pat. 2,599,761, especially columns 9-11; US. Pat. 2,725,359, especially columns 2, and 7-8; US. Pat. 2,767,142 especially column 4; US. Pat. 2,882,228, especially columns 6-7; US. Pat. 2,956,952, especially columns 3-5; US. Pat. 2,993,859, especially columns 2-3; US. Pat. 3,296,138, especially columns 6-10 and 12-20; and US. Pat. 3,357,920, especially columns -7. Other suitable lubricating base fluids are disclosed in Encyclopedia of Chemical Technology," Kirk-Othmer, second edition, volume 12, pages 557-616, especially pages 576-582, Interscience Publishers, 1967. More examples of metal working lubricant base fluids can be found in Metal Working Lubricants," E. L. H. Bastian, first edition, McGraw-Hill Book Co., Inc., 1951. All of the above patents and books including the references referred to therein are incorporated herein by reference.

The finished lubricant composition containing the above lubricating base fluids and the extreme pressure additives disclosed hereinbefore and specifically described hereinafter, can be used for lubricants for automobiles, aircraft, etc. as gear and bearing lubricants; as industrial metal working lubricants, e.g., for metal cutting and extrusion of steel, aluminum, titanium and its alloys, etc., (cutting fluids, drawing fluids, drawing compounds, extrusion lubricants, forging lubricants, rolling oils, machine tool lubricants, and other similar lubricants); and as fluids for the transmission of power, e.g., in car transmissions or hydraulic systems.

THE EXTREME PRESSURE ADDITIVE The extreme pressure additives of this invention when added to the lubricating base fluids hereinbefore described, improve the load-bearing properties of said lubricating base fluids.

The extreme pressure additives of this invention are characterized by the presence of a methylene or halo (chloro, iodo, or bromo) substituted methylene group. This methylene group is attached to two other groups, each of which can be either a phosphono (phosphonate diester), carboxylate ester, keto, cyano, phosphoryl (e.g., dialkylphosphine oxide), phenyl or substituted phenyl group. These groups are essential to the good performance of the extreme pressure additives. These groups are also important in modifying the solubility of the extreme pressure additives in various lubricating base fluids. For example, those groups whch contain alkyl groups can, by selecting the length of the alkyl groups, be modified to give various hydrophilic and hydrophobic properties to the extreme pressure additives. It will be noted that there is an optimum chain length for each extreme pressure additive for each lubricating base fluid.

The dihalo and monohalo extreme pressure additives of this invention can, in general, be prepared by reacting the non-halogenated compounds with the desired sodium hypohalite. See, e.g., O. T. Quimby et al., J. Or ganometallic Chemistry, 13, 199 (1968). The methylene diphosphonate esters can be prepared according to the teachings of US. Pat. 3,251,907. The dihalodicyanomethane extreme pressure additives can be prepared by reaction of the dicyanomethane with molecular halogen and subsequent decomposition of the alkali metal halide complex according to the teaching of Organic Synthesis, vol. 39, page 64, M. Tishler, ed. and L. Ramberg and S. Widequist, Arkiv Kerni, Mineral. GeoL, 12A, No. 22 (1937). The dihalodiphenylmethane compounds are available commercially. All of the extreme pressure additives can be prepared by known or analagous methods. The iodo compounds are generally a mixture of monoand diiodo compounds however.

Within the scope of the definition of the extreme pressure additives of this invention, there is a considerable variation in effectiveness with respect to extreme pressure properties and there is considerable variation with respect to other properties such as corrosivity, antiwear properties and, of course, solubility or dispersibility. The nonhalogenated methylenediphosphonate esters are the least corrosive of the additives. However, in general, they are also the least effective with respect to the extreme pressure properties. In general, the most effective extreme pressure additives are those which contain a dibromomethylene group. However, they tend to be more corrosive than the other additives. Among the more effective extreme pressure additives are the dichloro-, diiodoand dibromomethylenediphosphonates, the dibromomalonates, dibromomalononitrile, the tetrabromoglutarates, diphenyldichloromethane dibenzoyldibromomethane, and the dibromoand dichlorophosphonoacetates. The dichlorophosphonacetates are equal to or slightly better than the dibromophosphonoacetates. This is a surprising reversal of the general trend in which the dibromo compounds are more effective than the dichloro compounds. In general, the alkyl groups should contain from 1 to about 6 carbon atoms. However, in the case of the malonates, it is preferred that the alkyl groups contain at least about 5 carbon atoms since the malonates containing alkyl groups with less than about 5 carbon atoms tend to be more corrosive.

Certain of the extreme pressure additives have a difierent primary activity. For example, when the alkyl groups contain from about 7 to about 22 carbon atoms, they are effective antiwear additives. This is especially true of the methyleneand halomethylenediphosphonate esters.

Although the additives which contain long chain alkyl groups are more effective as antiwear additives, they also are as effective as the shorter chain compounds, on a molar basis, as extreme pressure additives and the longer chains are quite often more compatible with lubricants which are greases and waxes.

The iodo compounds, which are normally a mixture of monoand diiodo compounds, are good additives for metal working lubricants, especially lubricants which are used in the working of titanium and titanium alloys.

In general there will be from 1% to about 20% of the additive, preferably from about 2% to about 10% in the lubricant composition.

Mixtures of extreme pressure additives can also be used. A synergistic mixture of tetraalkyl dichloromethylenediphosphonate and tricresyl phosphate, a Well-known extreme pressure and anti-wear additive, is also preferred and is claimed in the copending application of Robert E. Wann, filed concurrently herewith, Ser. No. 763,006, now abandoned.

Finished lubricant compositions containing the extreme pressure additives of this invention can also contain other known additives, e.g., antioxidants, corrosion inhibitors, metal deactivators, viscosity index improvers, dispersing materials, dyes, thickeners, etc. Examples of antioxidants include 2,6-ditertiarybutyl-4-methylphenol; 2,6-ditertiarybutyl phenol; 2,6-ditertiaryamyl-4-methylphenol; 2,6-diisopropyl-4-methylphenol; phenylnaphthylamine; phenylenediamine; and diphenylamine.

This invention can be better understood by reference to the following examples which should not be taken as limiting the scope of the invention.

EXAMPLE I The following compositions were tested in a standard four ball tester for weld point (extreme pressure test) and wear scar (wear test). The weld point is defined as that pressure where the balls weld together in two successive runs of one minute under the indicated pressure. The wear scar is the average, based on three balls, of the average of both length and Width of the scars when the balls are run under a 40 kg. load for one hour at 1200 r.p.m. and at a temperature of All of the indicated additives in the following table were added to a Kendall SAE 10, parafiin base, additive free oil (lubricating base fluid) at the indicated level.

6 Composition 13-19, 23-25, and 40-51 show the effect' of varying the level of six representative extreme pressure additives of this invention. At a level of only C omp osition Tricresyl phosphate (TCP) 6. Benzyl disulfide 7- Hexachloroethane 9 Trichloroacetic acid 2 10 Randomly chlorinated paraffin, 11- Lead naphthenates e 12 Molybdenum disulfide 13 Tetraisopropyl dichloromethy]enediphosphonate (iPnChMDP).

14 iPHOlzh/I Percent Y weight H omvutnmmoucncnww O Weld Wear point scar 5 l 5 (MeiClgMD P) 21 Tetrakis(deeyl)dichloromethylenediphsphonatc 22 Tetrakis(stearyl)dichloromethylenediphosphonatc- 5 23 Tet-methyl dibromomethylenediphosphonate 5 (EMBHMDP). 24 EtiBr MDP 2. 5 25 EtlBliluDP 1 26 Tetraisopropyl dibromomethylenediphosphonate 5 (iP14Bl2l\L[D P) g; Tetrgisopropyl monobromomethylenediphosph0nate 5 0 5 Tetraisopropyl methylenediph0sphonate 5 30- Tetraethyl methylenediphosphonate u 5 31 Tetrakis(stearyl)mcthylenediphosphonate 5 (CiaMDP). 32 Diethyl trichloromethylphosphonate. 2 5 lPriClzMDP-i-CiaMDP (1:1) 10 34 Triethyl dichlorophosphonoaeetate 5 35 Triethyl dibromophosphonoacetate 5 36- Diphenylmethylene dichloride 5 37 Diethyl dibromomalonate 5 38- Diethyl dichloromalonate- 5 39 Diethyl malonate t. 5

Percent Weld Compo by point sltion Additive weight (kg.)

40 Di(n-pentyl) dibromomalonate (nC BrzMal) 5 800 41 do 3 500 42 2 380 43 1 280 44- 5 800 45 3 380 46- 2 320 47 1 280 48 5 800 49- 3 800 50 2 780 51 do 1 500 52- Tris(decyl) dibrornophosphonoacetate (CwBnPA) 5 240 53- Triethyl chlorophosphonoacetate (Et; CIPA) 5 260 54- Triethyl phosphonoacetate (Eta PA) 5 120 55- Tetrakis(decyl) methylenediphosphonate (CmMDP) 5 140 56 a Tetrabenzyl methylenediphosphonate (benzyl MD P) 5 120 57 Tetrabenzyl dichloromethylcnediphosphonate (Benzyl 5 220 ChMD P). 58. Tetreisopropyl diiodomethylencdiphosphonate 5 500 Dimethyl 3-ket0-2,2,4,4tetrabr0m0glutarate 5 800 Dibrornomalononitrile 5 800 61 Dibenzoyl dibromomethane 5 560 1 Base oil.

Very corrosive.

Compositions 2-12 and 32 demonstrate the effectiveness of certain representative prior art extreme pressure additives. It should be noted that, with the exception of the trichloroacetic acid and the diethyl trichloromethylphosphonate, the weld points are well under 400 kg. at an additive level of about 5%. The trichloroacetic acid and trichloromethylphosphonate, however, are quite corroslve.

about 1% they are still better than most conventional additives at a level of 5%.

Compositions 20-22 show the efiect of changing the length of the alkyl chain. The longer alkyl chains merely dilute the extreme pressure additive effect, since on a molar basis the improvements of the additives of Compositions 20-22 are about the same. There is a major ditference however in anti-wear properties since the tetrakis(decyl) and tetrakis(stearyl) additives provide a major improvement as demonstrated by the wear scar. The tetramethyl additive does not help the antiwear properties of the base fluid.

A comparison of Compositions 17 and 23; 14 and 26; and 37 and 38 shows that, in general, the dibromo additives are more efiective than the dichloro additives. This is especially true with the malonates. Similarly, a comparison of Compositions 14, 26 and 8 shows that for the particular tetraisopropyl methylenediphosphonate additives the diiodo derivative is better than the dibromo derivative which is better than the dichloro derivative. However, the ranking of the diiodo compound is undoubtedly aitected by the fact it contained a substantial amount of monoiodomethylenediphosphonate.

A comparison of Compositions 26, 27 and 29; 14, 28 and 29; 17 and 30; 21 and 55; 23 and 30; 37 and 39; 38 and 39; and 34, 53 and 54 shows the effect of going from a nonhalogenated to a monohalogenatcd to a dihalogenated extreme pressure additive having the same basic structure. In general the nonhalogenated compounds are not efl ective extreme pressure additives. However, surprisingly, the methylenediphosphonate esters have substantial extreme pressure activity. The monohalogenated compounds in general are not much better than the nonhalogenated compounds as extreme pressure additives and it is only with the dihalogenated compounds that the best extreme pressure activity is achieved. It is surprising that the change from monohalogenated to dihalogenated compounds would give such a tremendous increase in extreme pressure activity.

As Compositions 22 and 31 show the antiwear properties are affected only slightly by the presence or absence of the halogen atoms on a compound. Also, in Composition 33 a mixture of an extreme pressure additive (iPr Cl MDP) and an anti wear additive (C MDP) gives both good extreme pressure activity and anti-wear activity.

A comparison of the above compositions shows that the dichloroand dibromomethylenediphosphonates, the dichloroand dibromophosphonoacetates, the dibromomalonates, the dibromomalononitrile, and the tetrabromoglutarates give the best extreme pressure activity. The dichloromalononitn'le and the tetrachloroglutarates are also good. The diiodomethylenediphosphonates, dibenzoyldibromomethane, and the diphenylmethylene dichloride are also very good extreme pressure additives. These compounds, in general, will give a Weld point in the four ball test of at least about 400 kg. when used at the 5% level in this base fluid.

The dimethyl 3 keto 2,2,4,4-tetrabromoglutarate (Composition 59) is a difunctional dibromomethylene compound which shows that more than one YCX Y group can be present in a molecule of the extreme pressure additives of this invention.

Tetrabenzyl methylenediphosphonates are not very soluble in the base fluid of this example and accordingly are not as effective in this fluid as some of the other extreme pressure additives.

The diethyl dibromomalonate, e.g., Composition 37 and 48-51 are extremely corrosive. The dipentyl and diisopentyl esters of the dichloroand dibromomalonates, e.g., Compositions 40-47 are not corrosive.

In the following compositions, a comparison has been made between a base oil containing only the additives of this invention (Kendall base oil) and an oil containing a complete additive package including a corrosion inhibitor (Havoline). The corrosion inhibitor apparently has an adverse eflEect upon the extreme pressure activity, but the extreme pressure activity is still very good and the corrosiveness is minimized. Tetraisopropyl dichloromethylenediphosphonate is not as corrosive to steel as the other three additives and is included for comparison.

In the following compositions the base fluid was water.

Percent by Weld poin Additive Weight (kg 50 MerChMDP 5 EXAMPLE II The following compositions are excellent lubricants having better extreme pressure characteristics than the lubricating base fluid.

A dditive percent Lubricating by Extreme pressure additive base fluid Weight 1 Dibromodicyanomethane Allyl laurate 3. 5 2- Dichlorodicyanomethane Propyl propionate. 4 3. Dibromocyano(diethylphos- Trioctyl phosphate 5 phono)methane. 4- Dibromo(phenylmethyl) (di- Dioctyl carbonate" 5 methylphcsphoryl) methane. 5- Dichloro (diisopropylphos- Isopropyl myristate. 4

phone) decanoylmethane. 6 Ethyl diehlorocyanoacetate. Stearyl acetate 5 7 Dibromoeyanooctanoyl- Dibutyl ether of 3 methane. ethylene glycol. 8. Dichloro (butylmethylphos- Glycerol 3 phoryl) cyanomethane. 9. Diehlorodiphenylmethane Naphthalene 4 10- Dibromo (methylphenyl) Petrolatum 5 (dodecylphenyl) methane. ll- Bromochlero(decylphenyl) Parafiin wax 5 (diethylphenyDmethane. 12 Dichloro(biphenyl) 1:1 mixture of naph- 5 (naphthyDmethane. thalene and xylene. 13 Dibromo(chlorophenyl)-(3,4- Dioctylphthalate- 4 dinitrophenybmethane. l4- Dibrornobis(butylethylphos- Propylene glycol- 3 phoryl) methane. 15 Dibromo di (ethylbutyl ph 05- M ethyl ethyl ketone 4 phorylhnethane. l6. Chlorobromo(tetrachl0ro- Carnauba wax 6 stearylmethylphosphonio)- (tetrafluerostearyhnethylphosphonio)methane. 17. Dichloro(dinitrophehyl)- Tallow 5 (methyl dichlorooctylphcsphonio)methaue.

Additive percent Lubricating by Extreme pressure additive base fluid weight 18. Ethyl dibromo(dimethylphos- Stearyl alcohol 5 5 phonio)acetate.

10. Di(2-iodoacetyl)dibromo- 20% emulsion of 10 methane. tallow in water.

20.... Di(acetyl)dichloromethane.... Octyl tripropylene 5 glycol ether.

2L... Dipentyl monochloromalonate. Mineral oil (SAE 5 1O 22. Di(rnethylbcnzoyl) dibromo- Rosin 4 m hane.

23. Bromostearyl bromomethyl 1:1 phenol-formalde bromomalonate. hyde resin (M.W.

24.... Stearyl behenyl dichloro- Grease (lubricating 5 malonate. oil thickened with 1 soap).

25. Dodecenyl bromobenzyl Isopropyl laurate 6 dibromomalonate.

26.-- Iodobenzoyl (diiodoethyl- 1:1 mixture of iso- 5 phosphono) dichloromethane. propyl and alcohol.

27. Biphenylnaphthyldibromo- K r ene 4 methane.

28-.- Dihexyl chloromalonate Turbine oil 5 29--. Iodomethyl iodobenzyl 40% soybean oil in 10 dibromomalonate. Water emulsion.

30. Di(2-ethylhexyl) dibromo- Di(2-ethylhexyl) malonate. sebacate.

31--. Bromodicyanomethane....- u pen5i0n of 8 graphite in mineral oil (SAE 10). 32- Chlorodicyanomethanc Polyethyleneglycol 5 (M.W. 1,800). 33. Ethyl chlorocyanoacetate. Polypropyleneglycol 34. Chlorocyano(dl-isopropyl- Octyl th r of poly- 5 phospliono)methane. thyieneglycol 35.... Bromocyano(cetylmethyl- Di 2.ethylhexanoate 7 phosphorybmethane. of 11 ethylene glycol and propylene glycol (M.W. 6,000).

36.... Octadecenyl dibromost l te rrate 10 (butyloctadeccnylphosphoi'yl) acetate.

37- Dichloro(dimethylphos- 20% cottonseed oil in 10 PhO y p water emulsion with phono)methane. 5% alkyl(Cn-is) poly ethoxylate (9 moles) emulsifier.

38- Dibromodi(3,4-diiodophe Y Winterized and 5 methane. hardened (LV. 8)

soybean 011.

39- Tri benzyl bromochloro- Naphthenic hydro 5 phosphonoacetate. b n oil.

40- Tetra(tetrafluorostcary Fluorinated poly- 10 dibromomethylene dlphospropylene (MW. phonate. 1,000)

41- Dichloro di(3,4,5-trichlor0- D1. b ty1phthalatc- 4 phenyl)methane.

42- Dibrom0acetoylpr0D1O Y 1:1 mixture of dl-(Z- 4 methane. butoxyethyl) azelate 45 and di(rncthylcyclohexyl) adipate. 3- 0mop opy1dibromo-(4,5- The condensation 6 dichlorodecanoyl) acetate. product f propylene glycol, ethylene glycol, phthahc acid and sebacic acid in a 3:211 ratio (MW. 2,000).

44-.-. Dibromo liexanoyl (butyl- Th (j -C oxo 5 propylphosphono)methane. alcohol esters of phthalic acid.

45. Dichlorobenzoyl(ditolyl- Butyl ether of poly- 0 phosphcnohnethane. ethylene glycol 46. A 5:2 mixture of tri (decy1- A 3:1 mixture of butyl 7 phenyl) dichlorophosphono ether of polypropyacetate and N-phenyllene glycol M.W. alpha naphthylamine. 1,600) and diisooctyl adipate.

47. Bromochlorfl ecy p y Dioctylpentadecandl- 6 decanoylmethane. curboxylate.

4s. Dimethyl dibuty methy e Dimethylsillcone 5 diphosphonate. golloygier (M.W.

49.... Ethyldecylhexyl dibromo- Mineral oil (SAE 30)... 6

phosphonoacetate.

50. Dibromo[(2,3dichlorohe y1- Petroleum wax 10 phenyl) (3,4-difluoro benzyl)phosphono] [(5,6- dibromo-2-decenyl) methylphosphonolmethane.

51- 1:1 mixture of bis(2-ethy Kendall base oil 5 hexyl)dibromomalonate (SAE 10). and tetramethyldichloromethylenediphosphonate.

52.... 11:1 mixture of tetraisopropyl -...do 5

dibromomethylenediphos 7O phonate, triethyl dichloro phosphonacetate, and bis(2- ethylhexyDdichloromalonate.

53. Diacetyldibromomethane. Kengzilzbasc oil 5 54. Dibenzoyldiiodomethanc Cotton seed oil 10 75 Additive percent Lubricating by Extreme pressure additive base fluid weight 55. Bis(2-chloroethyl) dlchloro- Bis(2-ethylhexyl) 4 malonate. sebacate. 56. Dihexyl dibromomalonate..... Kendall base oil 5 (SAE 10). 57. Dibromomalononitrile Bis(2-ethylhexyl) 6 adipate. 58. n-D ecyl dibromocyanoacetate. Decyl decanoate 5 59 Tetrab enzyl dichloromethyl- Naphthalene 3 enediphosphonate. 60- Tris(p-nitrobenzyl)diiodo- Soybean oil 3 phosphonoacetate. 61 Bis[bis(fluoromethyD-Dhos- Parallin 4 phorylldichloromethane. 62. Bis(2,4-dichlorobenzoyl) di- Tripropylene glycol 5 bromomethane. didecanoate. 63 Dioleyl dibromomalonate. Stearyl stearate 8 64- Bls(p-dodecylbenzoyl) di- Stearyl benzoate 10 chloromethane. 65- Bromoiodomalononitrile 10% suspension of graph- 10 lte in kerosene. 66- Tetraisopropyl bromoiodo- Polypropylene glycol 6 methylenediphosphonate. (MW. 60 67- Dipentyl cyanodibromo- Polyethylene glycol 5 methylphosphonatc. (M.W. 900) 68. Tetrakis(aadibromopropyll Petroleum wax 6 dibromomethylenediphosphonate. 69 Bis (9,10-dichlorostearyl) bro- -do 15 momalonate. 70 Tris (2,2,2-trichloroet yl) 1 ,1,2-trichloroeth ane-- 6 dichlorophosphonoacetate. 71 Bromodicyanomethane Kerosene 3 7 Tetraethyl diiodomethylene- 20% emulsion of tal- 6 diphosphonate. low in water with 5% coconut alkyl polycthoxylate (15 moles ethylene oxide) emulsifier. 7 Pentyl dichlorocyanoacetate.. Kn)dall base oil (SAE 5 0 7 Dibromodiphenylmethane. Ken)da1l base oil (SAE 5 10 75 Bis (p-nitrophenyl) diiodowinterized and slight- 5 methane. 1y hardened (LV.

10) soybean oil. 76. cyanodibromophenylme- Tallow 8 thane. 77. Dicyelohexyl bromomalonate. Methyl stearate 5 78- Ethyl(perfluorophenyl)di- Fluorinated polyprog bromoacetate. gyfiege (M.W.

, 7 Tetramethyl dlchloromethyl- Polyvinyl chloride 5 enediphosphonate. (MW. 800). 80- Bis(2-ethylhexyl)dlbromo- Bis(2-ethylhexy1) 5 malonate. sebacate. 81- Bis (Z-methylbutyl) bromo- Bis (2-ethylhexyl) 5 malonate. adipate. 82. Bis(dioctylphosphoryl)dl- Propylene glycol dis- 4 chloromethane. tearate. 83 Dimethyl 3keto-2,2,4,4-tetra- Kendall base oil (SAE 5 bromoglutarate. 4 20) 84 Benzoyltrifluoroacetyldibro- Tetrapropylene glyg momethane. col dioctyl ether. 85 PentyKtrichloroacetyl) dl- Kendall base oil (SAE 5 chloroacetate. 20 86 Pentachlorobenzoylcyanodl- Paraffin 9 bromomethane. 87- (Diphenylphosphoryl) pro- Grease 12 pionylchloromethane. 88- Diphenylphosphorylcyanoio- Naphthalene 8 domethane. 89 Dipropyl phenyldichloro- Dloctyl phthalate..- 5

methylphosphonate. 90. Tetrakis(decyl) bromochloro- Kendall base oil (SAE 5 methylenediphosphonate. 30) 91 Tetrakis (stearyl) bromolodo- Tallow 5 methylenediphosphonate. 9 Bis(behenyl) dibromomalo- Behenyl behenate-. 20

nate. 93- Stearyl bromolodocyanoace- Stearyl acetate 10 tate. Divinyl cyanodlchloromethyl- Kendall base oil (SAE 5 phosphonate. 1 95 Dichlorornalononitrile 20% soybean oil in 5 water emulsion; 5% tallow fatty alcohol polyethoxylate (45 moles) emulsifier. 96- Tetraethyl dibromomethyl- Pentapropylene gly- 5 enediphosphonate. col dlundecanoate. 97 Tetraethyl dichloromethyl- 'lripropylene glycol 5 enedlphosphonate. didecanoate. 08 Tetraisopropyl dibromo- Havoline oil 5 methylenediphosphonate. 99 'Ietraisopropyl dichlorc- Bis(2-ethylhexyl) 5 methylenedlphosphonate. adipate. 100. Tetralsopropyl methylenedl- Tctrapropylcne gly- 5 phosphonate. col didodccanoate. 101 Tetraisopropyl bromomethyl- Kendall base oil (SAE 5 enediphosphonate. 10). 102. Diethyl dibromomalonate .do 5 103 Bis(benzoyl)dibromo- Cotton seed oil. 5

methane. 104. Dipentyl diiodomalonate Soybean oil 15 105 Pentyl 3-keto-2,2-dibromo- Kendall base oil (SAE 5 butyrate. 20)

EXAMPLE III lPl'iClzMDP lPHBrgMDP Magnesium i 0. 428 0. 210 0. 038 0. 045 0. 045 0. 173 1. 875 0. 195 0. 053 0. 555

EXAMPLE IV The following table compares the base oil of Example I with compositions containing the indicated amounts of the indicated additives in a four ball tester, a Timken tester, and a Falex tester. All three tests should be used to determine if the extreme pressure additive has wide utility. The representative additives of this invention are all clearly superior to the commercially available additives.

wherein each X is selected from the group consisting of chlorine," iodine" and bromineatoms', and wherein each R is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, alkenyl, haloalkyl, haloaryl, haloalkaryl, haloaral-kyl, haloalkenyl'and nitroaryl moieties containing from 1 to about 22 carbon atoms.

2. The composition of claim 1 wherein component (2) is selected from the group consisting of dibromomethylenediphosphonate esters, diiodomethylenediphosphonate esters, and dichloromethylenediphosphonate esters,

3. The composition of claim 2 wherein each R is an alkyl group containing from 1 to about 6 carbon atoms.

4. The composition of claim 1 wherein there is from about 1% to about of component (2).

5. The composition of claim 1 wherein there is from about 2% to about 10% of component (2).

6. The composition of claim 1 wherein each R is an alkyl group containing from about 7 to about 22 carbon atoms.

7. The composition of claim 1 wherein each R is an alkyl group contairn'ng from 1 to about 6 carbon atoms.

8. A composition of claim 1 wherein the lubricating base fluid is a lubricating oil.

Base 5% 5% 5% iPri 2.5% 1P1; 5% E134 2.5% Et 2.5% iPr; 2.5% Etl oil '1 OP SCL ClzMDP CIzM'DP ClzMDP ClgMDP BrzMDP BHMDP Four Ball:

Load Wear index 18. 4 26. 6 25. I 53. 6 33. 6 72. 9 62. 0 50. 3 105. 9 Weld point (kg) 112 112 224 316 251 501 355 251 562 1lk9lli beam load in pounds 3 12 18 55 65 75 65 Load in pounds 500 1, 250 1, 000 1 4, 500 1 4, 500 1 4, 500 1 4, 600 Torque in pound-inches 0) (65) (54) (60) 1 Capacity of instrument.

NOTE .All parts, percentages, and ratios herein are by weight unless otherwise sgecified. The four ball results in Example IV were obtained on a diflerent testing machine than the results in the other examples W R0 OR ieh caused the discrepancy.

References Cited UNITED STATES PATENTS 2,553,601 5/1951 Veatch et a1. 25249.3X 2,624,708 l/ 1953 Langer et a1. 25249.3X 2,634,288 4/ 1953 Boyer et al. 25249.8X 2,651,656 9/1953 Ladd et al. 25249.8X 2,825,693 3/1958 Beaubien et al. 25249.3X 2,957,931 10/1960 Hamilton et al. 2613-932X 3,422,021 l/ 1969 Roy 260932X 3,471,552 10/1969 Budnick 260-932X DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US. Cl. X.R. 

